CN107500300B - 一种有序介孔TiO2-SiO2纳米复合膜及其制备方法 - Google Patents
一种有序介孔TiO2-SiO2纳米复合膜及其制备方法 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002114 nanocomposite Substances 0.000 claims abstract description 24
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- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 108010025899 gelatin film Proteins 0.000 claims abstract description 17
- 230000001105 regulatory effect Effects 0.000 claims abstract description 15
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 14
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- 229910003082 TiO2-SiO2 Inorganic materials 0.000 claims abstract description 10
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
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- 239000004408 titanium dioxide Substances 0.000 claims description 8
- -1 titanium alkoxide Chemical class 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 7
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002280 amphoteric surfactant Substances 0.000 claims description 4
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- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
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- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
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- 229920000359 diblock copolymer Polymers 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical group [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical group [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 230000001360 synchronised effect Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- HNJXPTMEWIVQQM-UHFFFAOYSA-M triethyl(hexadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](CC)(CC)CC HNJXPTMEWIVQQM-UHFFFAOYSA-M 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000003053 toxin Substances 0.000 abstract description 9
- 231100000765 toxin Toxicity 0.000 abstract description 9
- 108700012359 toxins Proteins 0.000 abstract description 9
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- 230000015572 biosynthetic process Effects 0.000 abstract description 6
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- 239000000758 substrate Substances 0.000 description 4
- 241000195493 Cryptophyta Species 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
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- 238000006731 degradation reaction Methods 0.000 description 3
- 239000011363 dried mixture Substances 0.000 description 3
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- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- SRUWWOSWHXIIIA-UKPGNTDSSA-N Cyanoginosin Chemical compound N1C(=O)[C@H](CCCN=C(N)N)NC(=O)[C@@H](C)[C@H](C(O)=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)C(=C)N(C)C(=O)CC[C@H](C(O)=O)N(C)C(=O)[C@@H](C)[C@@H]1\C=C\C(\C)=C\[C@H](C)[C@@H](O)CC1=CC=CC=C1 SRUWWOSWHXIIIA-UKPGNTDSSA-N 0.000 description 2
- 229920002415 Pluronic P-123 Polymers 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HNUQMTZUNUBOLQ-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-(2-octadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO HNUQMTZUNUBOLQ-UHFFFAOYSA-N 0.000 description 1
- NLMKTBGFQGKQEV-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hexadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO NLMKTBGFQGKQEV-UHFFFAOYSA-N 0.000 description 1
- JKXYOQDLERSFPT-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-octadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO JKXYOQDLERSFPT-UHFFFAOYSA-N 0.000 description 1
- IEQAICDLOKRSRL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO IEQAICDLOKRSRL-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属无机膜材料技术领域,具体为一种有序介孔TiO2‑SiO2纳米复合膜及其制备方法。本发明采用联合、协同调控溶胶的酸度、成膜过程中周围环境温度、相对湿度、有机溶剂挥发速率等因素,使无机物前驱体分子及其低聚物与模板剂分子在溶剂挥发过程中于载体表面同步自组装,形成有序排列的有机–无机杂化的介观结构凝胶膜;再经无机物前驱体水解、交联、聚合,凝胶膜的烘干、焙烧去除模板剂、高温孔壁晶化等过程,制得有序介孔TiO2‑SiO2纳米复合膜。本发明方法可重复,合成条件可控。制备的复合膜介孔结构有序度高,热稳定性高,膜厚在一定范围内可控,在室温及紫外光照射下、于液相中,膜降解藻毒素的性能显著。
Description
技术领域
本发明属无机膜材料技术领域,具体涉及一种有序介孔TiO2-SiO2纳米复合膜及其制备方法;这种膜在室温与紫外光照射下,可快速、高效去除水中的藻毒素等污染物。
背景技术
有序介孔TiO2-SiO2纳米复合膜,因其具有可调的孔径、Ti/Si比、可变的孔道结构、高比表面积,更重要的是具有高的光稳定性(高的抗光腐蚀性能)、热稳定性、无毒、廉价、相对高的活性以及双功能性,在光催化、催化、光电转化、传感等领域具有广泛的潜在应用价值。因此,一直倍受关注与研究。在有序介孔TiO2-SiO2纳米复合膜制备过程中,溶胶的酸度、成膜过程中周围环境的温度、相对湿度、以及溶剂挥发速率等因素对其形成影响很大。酸度在溶胶的制备、载体表面溶胶液膜的制备、溶剂挥发到凝胶膜形成的整个过程中均有很大影响。温度对溶剂挥发的速率和模板剂的自组装的影响最为显著。相对湿度的高低主要影响TiO2、SiO2前驱体的水解、交联与聚合。载体表面的溶胶液膜通常很薄,有些甚至极薄,有机溶剂的挥发一般采用自然挥发,因此模板剂通常来不及组装成有序的介观结构,溶剂则早已挥发完,所以很难制备出有序的介孔膜,且重复性很差。通过联合、协同调控上述影响因素,特别是调控载体表面溶胶液膜中溶剂的挥发速率,可重复制备出有序介孔TiO2-SiO2纳米复合膜。目前这种膜材料以及这项技术均尚未见报道。
发明内容
本发明的目的是提出一种孔道排列有序度高、热稳定性好、比表面积大的有序介孔TiO2-SiO2纳米复合膜及其制备方法。
本发明采用联合、协同调控溶胶的酸度、成膜过程中周围环境温度、相对湿度、有机溶剂挥发速率等因素,使无机物前驱体分子及其低聚物与模板剂分子在溶剂挥发过程中于载体表面同步自组装,形成有序排列的有机–无机杂化的介观结构凝胶膜;再经无机物前驱体水解、交联、聚合,凝胶膜的烘干、焙烧去除模板剂、高温孔壁晶化等过程,制得有序介孔TiO2-SiO2纳米复合膜。其空间群结构为两维六方结构(p6m)、三维六方结构(P6 3 /mmc)、三维立方结构(Pm3n, Im3m, Ia3d);孔径范围为1~20 nm, BET比表面积为50~600 m2/g;膜厚度为20 nm~10 μm;热稳定性高于900℃,最高可达1100℃。膜层中二氧化钛为纳米晶粒,二氧化硅为无定型纳米颗粒;二氧化钛纳米晶粒与二氧化硅纳米颗粒相互连接、相间共存,形成一种非常独特的介孔膜骨架结构。这种膜在室温与紫外光照射下,能快速、高效去除水中的藻毒素等污染物。
本发明中,上述有序介孔材料为TiO2和SiO2两种组份组成的复合膜,晶相为锐钛矿或锐钛矿与金红石的混合相。
本发明提出的有序介孔TiO2-SiO2纳米复合膜的制备方法,包括研究溶胶的酸度、溶剂挥发过程中的相对湿度与温度、溶剂挥发的速率等制备条件。具体步骤如下:
(1)首先,将有机模板剂分子均匀分散于挥发性的有机溶剂内,得到溶胶;在搅拌下向上述溶胶内加入酸以调节酸度;
(2)然后,在搅拌下加入硅和钛的前驱体,继续搅拌形成均匀透明溶胶;
(3)将上述溶胶转移至已调控好温度、相对湿度、饱和溶剂蒸汽的样品柜内;
(4)采用浸渍-提拉法于载体表面覆盖一层溶胶液膜,然后将其置于样品架上;
(5)调控柜内溶剂蒸汽向外扩散的流量,以调控载体表面溶胶液膜中有机溶剂挥发的速率,使无机物分子及其低聚物与模板剂分子于载体表面同步自组装,形成有序排列的有机–无机杂化的介观结构凝胶膜,这个过程称为“同步自组装”;
(6)凝胶膜在柜内放置24~144小时,在此期间调控柜内温度和相对湿度,使钛和硅的前驱体水解、交联、聚合,并与载体表面结合形成稳固的介观结构凝胶膜;
(7)将负载型膜转移至烘箱内干燥6~120小时;
(8)焙烧除去模板剂,同时无机物种进一步交联、聚合并与载体表面键合,或再经更高温度处理,即得所需有序介孔TiO2-SiO2纳米复合膜;
(9)对于同一个载体从步骤(1)到步骤(8)可进行1~10次循环操作。
在室温与紫外光照射下,上述步骤获得的有序介孔TiO2-SiO2纳米复合膜于液相中对藻毒素表现出很好的降解性能。
步骤(1)中,模板剂均匀分散于有机溶剂内的步骤是:将模板剂分子溶于挥发性的有机溶剂的酸性溶液中,于密闭容器内,在磁力搅拌器上于10~70℃搅拌1~20小时,即可混合均匀;模板剂与有机溶剂的质量比为:1:(4~150)。加入的酸为盐酸、硫酸或硝酸等,每克模板剂加入酸的量为0.02~8克。
步骤(2)中,钛和硅的前驱体均匀分散于有机溶剂内的步骤是:将钛源和硅源在搅拌下滴入上述均匀混合的溶液中,在10~70℃继续搅拌1~18小时,即得均匀混合的透明溶胶。钛源和硅源的摩尔数与模板剂的质量(g)比为(0.001~0.09):1;加入的钛源为钛的烷氧化物、氯化物或其混合物,硅源为Si(OR)4。
步骤(3)中,将溶胶转入样品柜之前,控制柜内的温度为10~60℃、相对湿度为10~85%,溶剂蒸汽为饱和蒸汽。
步骤(4)中,在浸渍-提拉载体于其表面制备溶胶液膜过程中,柜内的温度、湿度、溶剂蒸汽同上。浸渍时间为0.1分钟至2小时,提拉速率为2~50 cm/分钟;样品片(或板)可以水平、竖直以及其它任意角度方式被置于样品架上。
步骤(5)中,载体表面溶胶液膜中有机溶剂的挥发采用受控挥发,即通过调控柜内溶剂蒸汽向外扩散的流量,使载体表面液膜中的有机溶剂逐渐挥发。
步骤(6)中,凝胶膜在柜内放置期间,温度和相对湿度在以下范围调控:温度为20~70℃,相对湿度为30~100%,溶剂蒸汽为零。
步骤(7)中,膜样品在烘箱内干燥的温度为60~100℃。
步骤(8)中,模板剂去除的方法是将干燥后的有机–无机复合凝胶膜置于管式炉或马福炉内,采用程序升温先于260~300℃保持2~5小时,然后于350 -400℃焙烧4~8小时,接着再于500~1100℃晶化2~30小时;升温速率为0.1~1℃/分钟;空气气氛。
本发明中,根据膜层的厚度或实际需要等,对于同一个载体从步骤(1)到步骤(8)可进行1~10次循环操作。
本发明制备的复合膜可用于光催化降解藻毒素,具体步骤为:将复合膜与藻毒素水溶液分别置于特制的石英反应器内(藻毒素浓度为1ng/L– 2 g/L),在室温下,先于暗处剧烈搅拌5– 90分钟,接着在紫外光照射下剧烈搅拌1– 600分钟,定时取定量样品,分析溶液中藻毒素含量,评价膜材料的吸附与降解性能。
本发明中,所用的模板剂可以是非离子型表面活性剂,也可以是阳离子型、阴离子型表面活性剂或两性表面活性剂。非离子型表面活性剂可以是三嵌段、两嵌段共聚物表面活性剂。如EO20PO70EO20 (Pluronic P123)、EO132PO50EO132 (Pluronic F108)、EO106PO70EO106(Pluronic F127)、EO123PO47EO123 (Pluronic F98)、EO39BO47EO39 (B50-66000)、C18H37EO20(Brij78)、C18H37EO10 (Brij 76)、C16H33EO20 (Brij 58)、C16H33EO10 (Brij 56)、C12H25EO23(Brij 35)等;阳离子型表面活性剂可以是十二烷基三甲基溴(氯)化铵、十四烷基三甲基溴(氯)化铵、十六烷基三甲基溴化铵(CTAB)、十六烷基三甲基氯化铵(CTAC)、十六烷基三乙基溴化铵(CTEAB)、十八烷基三甲基氯化铵(OTAC)等烷基卤化铵类;阴离子型表面活性剂为十六烷基磺酸钠;两性表面活性剂为聚氧乙烯烷基胺等。
本发明中,所用的挥发性有机溶剂可以是甲醇、乙醇、丙醇、丁醇等醇类,也可以是丙酮、乙氰、四氢呋喃等极性有机溶剂。
本发明中,所述的载体为玻璃片(或板)、氧化铝陶瓷片(或板)、单晶硅片、不锈钢片(或板);其表面为抛光面或非抛光面。
本发明中,所用的钛前驱体可以是钛烷氧化物【Ti(OR)4】,也可以是钛的氯化物【TiCl4】或它们的混合物;硅的前驱体为Si(OR)4。钛源与硅源的摩尔百分比为(99.9~0.1):(0.1~99.9)。
本发明合成方法可重复,合成条件可控。本发明的TiO2-SiO2纳米复合介孔膜的优点在于:孔道排列有序度高,热稳定性非常高,比表面积大,膜厚在一定范围内可调控;孔壁由二氧化钛纳米晶粒和二氧化硅纳米颗粒相互连接、相间共存组成;具有双功能性,表面具有强酸中心。本发明制备的有序介孔TiO2-SiO2纳米复合膜在光催化、催化、传感、光电转化、先进电池等领域有广泛的应用前景。例如通过光催化降解藻毒素。
附图说明
图1为550℃晶化20小时后玻璃片表面TiO2-SiO2纳米复合介孔膜的小角XRD谱。图中有一个极强的100衍射峰,表明介孔结构为高度有序的两维六方排列。
图2为550℃晶化20小时后玻璃片表面高度有序介孔TiO2-SiO2纳米复合膜的宽角XRD谱。谱图表明晶相为纳米锐钛矿相。
图3为550℃晶化20小时后玻璃片表面高度有序介孔TiO2-SiO2纳米复合膜的照片。
具体实施方式
以下实施例用来说明本发明,但不限制本发明申请请求保护的范围:
实施例1,高热稳定、两维六方结构有序介孔TiO2-SiO2纳米复合膜的合成:将2克P123模板剂溶于20~60克乙醇中,搅拌3~5小时。加入0.020~0.017摩尔钛酸乙酯或钛酸异丙酯或钛酸丁酯或四氯化钛,0.002~0.010摩尔正硅酸乙酯以及0.02~8克上述酸的一种,继续搅拌3 –5小时。将溶胶液转移至温度为10~20℃、相对湿度为15~25%、充满饱和乙醇蒸汽的柜内。采用浸渍-提拉法分别在玻璃片、陶瓷片、单晶硅片、不锈钢片表面覆盖一层溶胶液膜,然后将载有液膜的基底片水平置于样品架上。调控柜内乙醇蒸汽向外扩散的流量,载体表面的乙醇逐渐挥发,钛源与硅源分子及其低聚物与模板剂分子同步自组装,形成有序排列的有机–无机杂化的介观结构凝胶膜。排尽柜内乙醇蒸汽,将温度调为20~30℃、相对湿度调为60~70%。48~144小时后,将其转移至60~100℃的烘箱内烘干,之后将其置于管式炉或马福炉内。程序升温先在260℃保持3小时,然后在350℃焙烧4小时,接着以玻璃片为载体的膜在550℃晶化20小时,以陶瓷片、单晶硅片、不锈钢片为载体的膜在800℃分别晶化2小时,即得所需膜材料。膜厚为200 nm~1 μm,孔径为:4.0~8.0nm, 比表面积为:150~350 m2/g。二氧化钛晶相为锐钛矿,二氧化硅为无定型。在室温及紫外光照射下、于液相中,上述膜降解微囊藻毒素(MC–LR)的活性显著。
实施例2,高热稳定、三维六方结构有序介孔TiO2-SiO2纳米复合膜的合成:将1克F127模板剂溶于20~40克乙醇中,搅拌8~10小时。加入0.002– 0.012摩尔钛酸乙酯或钛酸异丙酯或钛酸丁酯或四氯化钛,0.001– 0.010摩尔正硅酸乙酯以及0.02~8克上述酸的一种,继续搅拌8– 10小时。将溶胶液转移至温度为20~30℃、相对湿度为40~50%、充满饱和乙醇蒸汽的柜内。采用浸渍-提拉法分别在玻璃片、陶瓷片、单晶硅片、不锈钢片表面覆盖一层溶胶液膜,然后将载有液膜的基片水平置于样品架上。调控柜内乙醇蒸汽向外扩散的流量,载体表面的乙醇逐渐挥发,钛源与硅源分子及其低聚物与模板剂分子同步自组装,形成有序排列的有机–无机复合的介观结构凝胶膜。除去柜内乙醇蒸汽,将温度调为30~40℃、相对湿度调为80~100%。48~120小时后,将其转移至60~100℃的烘箱内烘干,之后将其置于管式炉或马福炉内。程序升温先于280℃保持3小时,然后于350℃焙烧6小时,接着以玻璃片为载体的膜在550℃晶化20小时,以陶瓷片、单晶硅片、不锈钢片为载体的膜在900℃分别晶化2小时,即得所需膜材料。膜厚:100 nm~3 μm;孔径为:4.0~8.0nm, 比表面积为:120~260 m2/g。二氧化钛晶相为锐钛矿,二氧化硅为无定型。在室温及紫外光照射下、于液相中,该类膜快速、高效降解微囊藻毒素(MC–LR)。
实施例3,高热稳定、三维立方结构有序介孔TiO2-SiO2纳米复合膜的合成:将1.5克F108模板剂溶于40~50克乙醇中,搅拌6 –8小时。加入0.015~0.025摩尔钛酸乙酯或钛酸异丙酯或钛酸丁酯或四氯化钛,0.015– 0.001摩尔正硅酸乙酯以及0.02~8克上述酸的一种,继续搅拌10~12小时。将溶胶液转移至温度为35~45℃、相对湿度为70~80%、充满饱和乙醇蒸汽的柜内。采用浸渍-提拉法分别在玻璃片、陶瓷片、单晶硅片、不锈钢片表面覆盖一层溶胶液膜,然后将载有液膜的基片置于样品架上。调控柜内乙醇蒸汽向外扩散的流量,基片表面的乙醇逐渐挥发,钛源与硅源分子及其低聚物与模板剂分子同步自组装,形成有序排列的有机–无机杂化的凝胶膜。排空柜内乙醇蒸汽,将温度调为50~60℃、相对湿度调为80~100%。48~120小时后,将其转移至60~100℃的烘箱内烘干,之后将其分别置于管式炉或马福炉内。程序升温先于280℃保持3小时,然后于350℃焙烧5小时,接着以玻璃片为载体的膜在550℃晶化25小时,以陶瓷片、单晶硅片、不锈钢片为载体的膜在850℃分别晶化2小时,即得所需膜材料。膜厚为:20 nm~1.3 μm;孔径为:4.0~8.0 nm, 比表面积为:180~310 m2/g。二氧化钛晶相为锐钛矿,二氧化硅为无定型。在室温及紫外光照射下、于液相中,此类膜对微囊藻毒素(MC–LR)显示出独特的降解性能。
Claims (7)
1.一种有序介孔TiO2-SiO2纳米复合膜的制备方法,其特征在于,具体步骤如下:
(1)首先,将有机模板剂分子均匀分散于挥发性的有机溶剂内,得到溶胶;在搅拌下向上述溶胶内加入酸以调节酸度;
(2)然后,在搅拌下加入硅和钛的前驱体,继续搅拌形成均匀透明溶胶;
(3)将上述溶胶转移至已调控好温度、相对湿度、饱和溶剂蒸汽的样品柜内;
(4)采用浸渍-提拉法于载体表面覆盖一层溶胶液膜,然后将其置于样品架上;
(5)调控柜内溶剂蒸汽向外扩散的流量,以调控载体表面溶胶液膜中有机溶剂挥发的速率,使无机物分子及其低聚物与模板剂分子于载体表面同步自组装,形成有序排列的有机–无机杂化的介观结构凝胶膜,这个过程称为“同步自组装”;
(6)凝胶膜在柜内放置24 – 144小时,在此期间调控柜内温度和相对湿度,使钛和硅的前驱体水解、交联、聚合,并与载体表面结合形成稳固的介观结构凝胶膜;
(7)将负载型膜转移至烘箱内干燥6 – 120小时;
(8)焙烧除去模板剂,同时无机物种进一步交联、聚合并与载体表面键合,或再经更高温度处理,即得所需有序介孔TiO2-SiO2纳米复合膜;
其中,所述的有机模板剂为非离子型表面活性剂,或者为阳离子型表面活性剂,或者为阴离子型表面活性剂,或者为两性表面活性剂;
所述的钛源为钛的烷氧化物、氯化物或其混合物,硅源为Si(OR)4;
步骤(1)中,模板剂均匀分散于有机溶剂内的步骤是:将模板剂分子溶于挥发性的有机溶剂的酸性溶液中,于密闭容器内,在磁力搅拌器上于10 – 70℃搅拌1 – 20小时;模板剂与有机溶剂的质量比为:1:(4 – 150);加入的酸为盐酸、硫酸或硝酸,每克模板剂加入酸的量为0.02 – 8克;
步骤(2)中,钛和硅的前驱体均匀分散于有机溶剂内的步骤是:将钛源和硅源在搅拌下滴入上述均匀混合的溶液中,在10 – 70℃继续搅拌1 – 18小时,即得均匀混合的透明溶胶;钛源和硅源的摩尔数与模板剂的质量比为(0.001 – 0.09):1;加入的钛源为钛的烷氧化物、氯化物或其混合物,硅源为Si(OR)4;
步骤(3)中,溶胶转入样品柜之前,控制柜内的温度为10 – 60℃、相对湿度为10 –85%,溶剂蒸汽为饱和蒸汽;
步骤(4)中,在浸渍-提拉载体于其表面制备溶胶液膜过程中,柜内的温度、湿度、溶剂蒸汽同步骤(3);浸渍时间为0.1分钟至2小时,提拉速率为2 – 50 cm/分钟;样品片以水平、竖直以及其它任意角度方式置于样品架上;
步骤(5)中,载体表面溶胶液膜中有机溶剂的挥发采用受控挥发,即通过调控柜内溶剂蒸汽向外扩散的流量,使载体表面液膜中的有机溶剂逐渐挥发;
步骤(6)中,凝胶膜在柜内放置期间,温度和相对湿度在以下范围调控:温度为20 – 70℃,相对湿度为30 – 100%,溶剂蒸汽为零;
步骤(7)中,膜样品在烘箱内干燥的温度为60 – 100℃;
步骤(8)中,模板剂去除的方法是将干燥后的有机–无机复合凝胶膜置于管式炉或马弗炉内,采用程序升温先于260 – 300℃保持2 – 5小时,然后于350-400℃焙烧4 – 8小时,接着再于500 – 1100℃晶化2 – 30小时;升温速率为0.1 – 1℃/分钟;空气气氛。
2.根据权利要求1所述的制备方法,其特征在于,对于同一个载体从步骤(1)到步骤(8)可进行1 – 10次循环操作。
3.根据权利要求1或2所述的制备方法,其特征在于,所述非离子型表面活性剂为下述三嵌段、两嵌段共聚物表面活性剂之一种或几种:EO20PO70EO20、EO132PO50EO132、EO106PO70EO106、EO123PO47EO123、EO39BO47EO39、C18H37EO20、C18H37EO10、C16H33EO20、C16H33EO10、C12H25EO23。
4.根据权利要求3所述的制备方法,其特征在于,所述阳离子型表面活性剂为十二烷基三甲基溴化铵、十四烷基三甲基溴化铵、十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十六烷基三乙基溴化铵或十八烷基三甲基氯化铵;阴离子型表面活性剂为十六烷基磺酸钠;两性表面活性剂为聚氧乙烯烷基胺。
5.根据权利要求1、2或4所述的制备方法,其特征在于,所用的挥发性有机溶剂为甲醇、乙醇、丙醇、丁醇、丙酮、乙氰、四氢呋喃中的一 种。
6.根据权利要求1、2或4所述的制备方法,其特征在于,所述的载体为玻璃片、氧化铝陶瓷片、单晶硅片、不锈钢片;其表面为抛光面或非抛光面。
7.由权利要求1-6之一所述制备方法制备得到的有序介孔TiO2-SiO2纳米复合膜,其空间群结构为两维六方结构、三维六方结构、三维立方结构;孔径范围为1 – 20 nm, BET比表面积为50 – 600 m2/g;膜厚度为20 nm – 10 μm;热稳定性高于900℃,最高达1100℃;膜层中二氧化钛为纳米晶粒,二氧化硅为无定型纳米颗粒;二氧化钛纳米晶粒与二氧化硅纳米颗粒相互连接、相间共存,形成独特的介孔膜骨架结构。
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